基于智能手机的便携式毛细管电泳装置检测消毒剂中2种季铵盐

doi:10.3724/SP.J.1123.2021.04030

摘要/Abstract

摘要：

现有的小型毛细管电泳(CE)装置仍采用平板或计算机进行数据处理和分析,其便携性仍存在明显不足。针对这一问题,发展了一种基于智能手机的CE装置,实现了真正的便携式定量分析。该装置集成了电容耦合式非接触式电导检测(C⁴D)和蓝牙通信功能,并提供了手机界面软件。通过手机界面软件,不仅可以控制CE装置的电泳运行,还可以实时接收C⁴D检测器发出的数据信息,显示电泳图谱和进行数据处理。该装置尺寸为20 cm×20 cm×15 cm,重量为2 kg。为了验证所设计装置的性能,采用季铵盐(QAs)消毒剂(十二烷基二甲基苄基溴化铵(DDBAB)和十二烷基三甲基溴化铵(DTAB))作为分析对象。实验数据表明,DDBAB和DTAB线性范围分别为20~1000和30~1000 μmol/L,线性回归方程的相关系数(R²)分别为0.9995和0.9989,检出限(LOD)分别为10和13 μmol/L,日内相对标准偏差(RSD, n=3)分别为1.9%和2.7%。另外实验对DDBAB和DTAB混合离子液进行了测试,在8 min内可实现基线分离。最后,对现场使用的新洁尔灭消毒液中QAs进行了加标回收试验,DDBAB和DTAB的回收率分别为100.5%~101.5%和96.2%~99.3%。研究结果表明,所开发CE装置具有线性好、LOD低、重复好、准确性高,尤其便携好等优点,可用于消毒液中QAs现场定量检测。

关键词: 毛细管电泳, 电容耦合式非接触电导检测, 基于智能手机的便携式装置, 季铵盐, 消毒剂

Abstract:

The existing miniature capillary electrophoresis (CE) devices use a tablet or a computer for data processing and analysis, which hinders their portability. In order to solve this problem, a smartphone-based CE device was proposed, which allowed for real portable quantitative analysis. The device integrated the functions of capacitively coupled contactless conductivity detection (C⁴D) and Bluetooth communication. Furthermore, a Kotlin language-based application with a user-friendly interface was developed. The application could not only control the electrophoresis run in the CE device but also receive the data from the C⁴D detector in real time, display the electrophoretogram, and process the data. The peak areas could be calculated automatically on the smartphone, and the migration time could be obtained. The size of the developed device was 20 cm×20 cm×15 cm, and its weight was 2 kg. Quaternary ammonium salts (QAs) in disinfectors (dodecyl dimethyl benzyl ammonium bromide (DDBAB) and dodecyl trimethyl ammonium bromide (DTAB)) were used as the analytes to verify the performance of the developed device. The experimental data showed that the linear ranges of DDBAB and DTAB were from 20 to 1000 and from 30 to 1000 μmol/L, respectively. The correlation coefficients (R²) of DDBAB and DTAB were 0.9995 and 0.9989, respectively, indicating good linearity between the peak area and concentration. The limits of detection (LODs) of DDBAB and DTAB were 10 and 13 μmol/L, respectively. The intra-day relative standard deviations (RSDs, n=3) of DDBAB and DTAB were 1.9% and 2.7% respectively, revealing good repeatability. In addition, a mixture of DDBAB and DTAB was tested. Two QAs were separated within 8 min, showing good selectivity. Finally, QAs in a bromo geramine disinfector used in the field were tested to further validate the performance of the designed device. The recoveries of DDBAB and DTAB were 100.5%-101.5% and 96.2%-99.3%, respectively, indicating good accuracy. The developed device has the advantages of good linearity, low LOD, good repeatability, high accuracy, and real portability, and it can be used for the quantitative detection of QAs in disinfectors.

Key words: capillary electrophoresis (CE), capacitively coupled contactless conductivity detection (C⁴D), smartphone-based portable device, quaternary ammonium salts (QAs), disinfector

中图分类号:

O658

王源豫, 张瑞华, 张强, 曹成喜, 樊柳荫, 刘伟文. 基于智能手机的便携式毛细管电泳装置检测消毒剂中2种季铵盐[J]. 色谱, 2021, 39(11): 1151-1156.

WANG Yuanyu, ZHANG Ruihua, ZHANG Qiang, CAO Chengxi, FAN Liuyin, LIU Weiwen. Determination of two quaternary ammonium salts in disinfector by portable capillary electrophoresis device based on smartphone[J]. Chinese Journal of Chromatography, 2021, 39(11): 1151-1156.

图/表 7

图1 基于智能手机的便携式CE-C4D装置(a)高压电源与检测模块和(b)手机控制器

Fig. 1 Smartphone-based portable capillary electropho- resis with capacitively coupled contactless conductivity detection (CE-C4D) device with (a) high voltage supply and detection module and (b) smartphone controller MCU: microcontroller unit; DAC: digital to analog converter.

图2 便携式CE-C4D装置示意图

Fig. 2 Schematic diagram of CE-C4D device a. capillary; b. high voltage supply; c. anode background electrolytes (BGE) vial; d. cathode BGE vial; e. sample vial; f. C4D sensor.

表1 两种季铵盐的线性方程、相关系数、线性范围、检出限及相对标准偏差

Table 1 Linear equations, correlation coefficients (R2), liner ranges, LODs and RSDs of two quaternary ammonium salts (QAs)

Compound	Regression equation	R²	Linear range/(μmol/L)	LOD/(μmol/L)	RSD (n=3)/%
DDBAB	Y=6.2478X+0.0057	0.9995	20-1000	10	≤1.9
DTAB	Y=5.3290X-0.0940	0.9989	30-1000	13	≤2.7

图3 (a)背景液、(b)DDBAB、(c)DTAB及其(d)混合离子溶液的电泳图谱

Fig. 3 Electrophoretograms of (a) background electrolytes, (b) DDBAB, (c)DTAB and (d) their mixed ion solution a. 25 mmol/L Lac-β-Ala; b. 25 mmol/L Lac-β-Ala with 1 mmol/L DDBAB; c. Lac-β-Ala with 1 mmol/L DTAB; d. 25 Lac-β-Ala with 1 mmol/L DDBAB and 1 mmol/L DTAB. Peak identifications: * system peaks.

图4 新洁尔灭消毒液中QAs的重复性测试

Fig. 4 Repeatability test of QAs in bromo geramine disinfector

表2 新洁尔灭消毒液中DDBAB与DTAB的加标回收率(n=5)

Table 2 Spiked recoveries of DDBAB and DTAB in bromo geramine disinfector (n=5)

Compound	Background/ mg	Spiked/ mg	Found/ mg	Recovery/ %	RSD/ %
DDBAB	1.07	0.8	1.882	101.5	1.47
		1	2.081	100.5	2.13
		1.2	2.286	101.3	1.19
DTAB	0	0.8	0.794	99.3	1.17
		1	0.962	96.2	1.35
		1.2	1.187	98.9	2.29

表3 本文开发的CE-C4D装置与现有装置的比较

Table 3 Comparison of developed CE-C4D device with existed devices

Device	LOD/ (μmol/ L)	Size/ (cm×cm ×cm)	Smartphone controlled	Ref.
Automated CE-C⁴D	5	45×35×15	no	[17]
CE-C⁴D of small volumes	0.36	20×33×17	no	[19]
biological fluid
CDC-based CE-C⁴D	12	not reported	no	[20]
Smartphone-based	10	20×20×15	yes	this
CE-C⁴D				work

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